Choksi Tej, Majumdar Paulami, Greeley Jeffrey P
Davidson School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN, 47906, USA.
Angew Chem Int Ed Engl. 2018 Nov 19;57(47):15410-15414. doi: 10.1002/anie.201808246. Epub 2018 Oct 23.
Linear scaling relationships (SRs), which relate binding energies of adsorbates across a space of catalyst surfaces, have been extensively explored for metal and oxide surfaces, but little is known about their properties at interfaces between metal nanoparticles and oxide supports, which are ubiquitous in heterogeneous catalysis. Using periodic DFT calculations, scaling principles are extended to bifunctional Au/oxide interfaces. Adopting a Au nanorod on doped MgO (100) as a model, SRs for species participating in water gas shift, methanol synthesis, and oxidation reactions are reported. SR slopes are not constrained by the bond order conservation rule postulated for metals, oxides, and zeolites, potentially permitting greater flexibility in catalyst design strategies. The deviation from bond counting, along with the physical origin of scaling behavior at interfaces, are explored using a conceptual framework involving electrostatic interactions at the Au/oxide interface.
线性标度关系（SRs），即关联催化剂表面空间内吸附质结合能的关系，已在金属和氧化物表面得到广泛研究，但对于金属纳米颗粒与氧化物载体界面处的性质却知之甚少，而这种界面在多相催化中普遍存在。通过周期性密度泛函理论（DFT）计算，标度原理被扩展到双功能金/氧化物界面。采用掺杂氧化镁（100）上的金纳米棒作为模型，报道了参与水煤气变换、甲醇合成和氧化反应的物种的SRs。SR斜率不受为金属、氧化物和沸石假定的键序守恒规则的限制，这可能使催化剂设计策略具有更大的灵活性。利用一个涉及金/氧化物界面静电相互作用的概念框架，探索了与键计数的偏差以及界面处标度行为的物理起源。
